Scaled nanotube electrode for low power multistage atomic switch

ABSTRACT

A method of forming a memory device that includes depositing a first dielectric material within a trench of composed of a second dielectric material; positioning a nanotube within the trench using chemical recognition to the first dielectric material; depositing a dielectric for cation transportation within the trench on the nanotube; and forming a second electrode on the dielectric for cation transportation, wherein the second electrode is composed of a metal.

BACKGROUND Technical Field

The present invention generally relates to electronics having amicroscale or less, and more particularly to atomic switches.

Description of the Related Art

An atomic switch is a nanoionic device that controls the diffusion ofmetal ions and their reduction/oxidation processes in the switchingoperation to form/annihilate a metal atomic bridge, which is aconductive path between two electrodes in an ON-state. Since metal atomscan provide a highly conductive channel even if their size is in thenanometer scale, atomic switches may enable downscaling to very smalldevice dimensions. Two-terminal atomic switches have the potential foruse in memories and programmable switches. Recent development oftwo-terminal atomic switches that use a metal oxide as the ionicconductive material, in which a metal atomic bridge is formed, hasenabled the integration of atomic switches with complementarymetal-oxide-semiconductor (CMOS) devices.

SUMMARY

In accordance with one embodiment, an switch, e.g., atomic switch, isprovided that employs a nanotube structure, e.g., single walled carbonnanotube (SWCNT), for at least one electrode of the switch. In oneembodiment, the switch includes a carbon nanotube present on a substrateto provide a first electrode of the switch. A dielectric for cationtransportation is present on the first electrode. A second electrodecomposed of a metal is present no a surface of the dielectric for cationtransportation that is opposite the surface of the dielectric for cationtransportation that is in contact with the first electrode.

In another aspect, a method of forming a memory device is provided. Inone embodiment, the method includes positioning a carbon nanotube withina trench of an oxide containing material. The trench is patterned toprovide vias to the carbon nanotube, wherein each via to the carbonnanotubes defines a memory cell. A dielectric for cation transportationis deposited within the trench on the carbon nanotube. A secondelectrode is formed on the dielectric for cation transportation, whereinthe second electrode is composed of a metal.

In another embodiment, a method of forming a memory device is providedthat includes depositing a second dielectric material within a trench ofcomposed of a first dielectric material; and positioning a nanotubewithin the trench using chemical recognition to the second dielectricmaterial. The trench is patterned to provide vias to the carbonnanotube, wherein each via to the carbon nanotubes defines a memorycell. A dielectric for cation transportation is deposited within thetrench on the carbon nanotube. A second electrode is formed on thedielectric for cation transportation, wherein the second electrode iscomposed of a metal.

These and other features and advantages will become apparent from thefollowing detailed description of illustrative embodiments thereof,which is to be read in connection with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The following description will provide details of preferred embodimentswith reference to the following figures wherein:

FIG. 1 is a side cross-sectional view depicting an atomic switch thatmay be employed in a memory application, in which the inert electrode ofthe atomic switch is provided by a carbon nanotube, in accordance withan embodiment of the present disclosure.

FIG. 2 is a side cross-sectional view depicting atoms having acomposition similar to the reactive electrode of the atomic switchdepicted in FIG. 1 during a first stage of operation.

FIG. 3 is a side cross-sectional view depicting atoms having acomposition similar to the reactive electrode of the atomic switchdepicted in FIG. 1 during a second stage of operation.

FIG. 4A is a side cross-sectional view of a method step for forming oneembodiment of the atomic switch that is depicted in FIGS. 1-3, in whichthe method includes positioning a nanotube within a trench of an oxidecontaining material, in accordance with one embodiment of the presentdisclosure.

FIG. 4B is a top down view of the structure depicted in FIG. 4A, inwhich the side cross-sectional view depicted in FIG. 4A is along sectionline A-A in FIG. 4B.

FIG. 5 is an illustration depicting chemical recognition for engagingthe carbon nanotube to a dielectric positioned within the trench.

FIG. 6 is a side cross-sectional view depicting patterning a via to thecarbon nanotube, wherein the via to the nanotube defines a memory cell,in accordance with one embodiment of the present disclosure.

FIG. 7 is a side-cross sectional view depicting depositing a dielectricfor cation transportation within the via on the carbon nanotube, inaccordance with one embodiment of the present disclosure.

DETAILED DESCRIPTION

Detailed embodiments of the claimed structures and methods are disclosedherein; however, it is to be understood that the disclosed embodimentsare merely illustrative of the claimed structures and methods that maybe embodied in various forms. In addition, each of the examples given inconnection with the various embodiments is intended to be illustrative,and not restrictive. Further, the figures are not necessarily to scale,some features may be exaggerated to show details of particularcomponents. Therefore, specific structural and functional detailsdisclosed herein are not to be interpreted as limiting, but merely as arepresentative basis for teaching one skilled in the art to variouslyemploy the methods and structures of the present disclosure. Forpurposes of the description hereinafter, the terms “upper”, “lower”,“right”, “left”, “vertical”, “horizontal”, “top”, “bottom”, andderivatives thereof shall relate to the embodiments of the disclosure,as it is oriented in the drawing figures. The terms “positioned on”means that a first element, such as a first structure, is present on asecond element, such as a second structure, wherein interveningelements, such as an interface structure, e.g. interface layer, may bepresent between the first element and the second element. The term“direct contact” means that a first element, such as a first structure,and a second element, such as a second structure, are connected withoutany intermediary conducting, insulating or semiconductor layers at theinterface of the two elements.

The methods and structures disclosed herein provide a structure andmethod for making an ultralow power atomic switch, where one electrodeis provided by a nanotube. Neuromorphic computing can require memorydevices with multiple states and operating at low power. It has beendetermined that these characteristics can be met with an atomic switch.In an atomic switch, switching occurs in a vacuum/dielectric gap throughmetal ion diffusion and redox reactions. Atomic switch devices canachieve both low power and quantized multiple conductance levels.However, it has been determined that with a planar electrode, the widthof the filament will be very difficult to control on the atomic scale.It has further been determined that when the atomic switch having aplanar electrode for the inert electrode of the device in a memoryapplication that the difficulty in controlling the dimensions of theplanar electrode can lead to unreliable multistage storage. In view ofthe aforementioned difficulties, a structure and method for making anultralow power atomic switch, in which the atomic switch includes anelectrode, i.e., inert anode, composed of a nanotube, such as a carbonnanotube, e.g., single walled carbon nanotube (SWCNT). The size of thenanotube, e.g., having a diameter of 1 nm, provides a surface foraddition atoms of metal diffused from a metal electrode. For example,the extreme size of the nanotube provides a surface for adding silver(Ag) and/or copper (Cu) cation atoms one by one in contact with thefilament provided by the carbon nanotube. Some embodiments of themethods and structures of the present disclosure are now described withreference to FIGS. 1-7.

FIGS. 1A-3 depict one embodiment of an atomic switch 100 in accordancewith the present disclosure. The atomic switch 100 may include a carbonnanotube 10 is present on a substrate to provide a first electrode ofthe switch. The carbon nanotube 10 typically provides the inertelectrode of the switch. As used herein, the term “nanotube” is meant toinclude single walled and multi-walled nanotubes. In one embodiment, thecarbon nanotube 10 is a single walled carbon nanotube that provides theinert electrode of the atomic switch 100, in which the atomic switch 100can be used in memory applications. In one embodiment, a carbon nanotube10 is at least one graphene layer wrapped into a cylinder. In oneembodiment, a single wall carbon nanotube 10 is a graphene rolled upinto a seamless cylinder with diameter of the order of a nanometer. Amulti-walled carbon nanotube 10 is a plurality of graphene sheets rolledup into a seamless cylinder with diameter of the order of a nanometer.More specifically, the diameter D1 of the carbon nanotube 10 may beequal to 1 nm or 2 nm or a value between 0.5 nm and 3 nm. As depicted inFIGS. 1A and 1B, the longest dimension L1 of the carbon nanotube 10 mayextend along a dimension that is perpendicular to the top metalelectrode that could serve as a word/bit line in a cross-bar arraystructure. In one embodiment the greatest dimension L1 of the carbonnanotube 10, as used in accordance with the methods and structuresdescribed herein ranges from about 0.5 nanometers to about 10 microns.In another embodiment, the greatest dimension L1 of a single wallnanotube ranges from about 100 nanometers to about 10 millimeters. Inone embodiment, the nanotubes used in accordance with the methods andstructures disclosed herein have an aspect ratio of length, i.e.,longest dimension L1, to width, i.e., diameter D1, on the order ofapproximately 1,000:1.

In one example, the carbon nanotube 10 that provides the electrode forthe atomic switch 100 is a single walled carbon nanotube (SWCNT) havinga diameter ranging from 1 nm to 2 nm, and a length that ranges fromabout 0.5 nanometers to about 50 microns.

In one embodiment, carbon nanotubes 10 that are used in accordance withthe methods and structure disclosed herein are originally produced bylaser ablation have a high purity. The carbon nanotubes disclosed hereinmay also be originally produced using chemical vapor deposition. In oneembodiment, the carbon nanotubes 10 may have a high purity on the orderof about 90% carbon or greater. In another embodiment, the carbonnanotubes 10 may have a high purity on the order of about 95% to about99% carbon. In an even further embodiment, the carbon nanotubes 10 havea purity that is greater than 99% carbon.

The carbon nanotubes 10 are typically present within a trench defined bysidewalls of silicon oxide, and on a hafnium containing layer 15 thatthe carbon nanotube is aligned with by chemical recognition. In someembodiments, the hafnium containing layer 15 may be composed of hafniumoxide (HfO₂). It is noted that hafnium oxide (HfO₂) is only one exampleof a material layer that the carbon nanotube may be aligned to usingchemical recognition. In other examples, the carbon nanotubes 10 may bechemically aligned with an aluminum oxide or silicon nitride layer thatis present within a trench of silicon oxide. As will be described below,the chemical recognition process that aligns the carbon nanotube to thehafnium containing material (or aluminum containing material) isselective to the hafnium containing material, e.g., hafnium oxide(HfO₂), (or aluminum containing material (e.g., aluminum oxide (Al₂O₃)),and is non selective to the silicon oxide material of the trench. Thisprovides that the carbon nanotube 10 be aligned with the hafniumcontaining layer 15 at the base of the trench, and is in direct contactwith the hafnium containing layer 15. The carbon nanotube 10 is notpresent on the trench sidewalls, which are composed of silicon oxide. Insome embodiments, because a length of hafnium oxide is positioned down alength of the trench, the length of the carbon nanotube 10 is alignedwith the length of the trench, i.e., the length L1 of the carbonnanotube 10 is parallel with the length of the trench.

Although not depicted in the supplied pictures, the silicon oxide layerthat the provides the trenches, in which the hafnium containing layer15, and therefore the carbon nanotubes 10, are present is positioned ona supporting substrate. The supporting substrate may be a dielectricmaterial, such as glass; polymeric material; or a semiconductormaterial, such as a type IV semiconductor, e.g., silicon, or a typeIII-V semiconductor material, e.g., gallium arsenide.

Still referring to FIG. 1, the memory cells are defined by viasextending to the carbon nanotubes 10. The sidewalls of the vias areprovided by an oxide layer 5, e.g., silicon oxide (SiO₂) layer. In someembodiments, a dielectric for cation transportation 20 is present on thefirst electrode that is provided by the carbon nanotube 10. In the finalstructure the dielectric for cation transportation 20 is present betweenan inert electrode that is provided by the carbon nanotube 10, and areactive electrode 25 that is provided by a metal, such as silver (Ag)or copper (Cu). In operation, the mobile ions diffusing from thereactive electrode 25, are contained in the dielectric for cationtransportation 20, and form a bridge between the first and secondelectrodes to change the conductance between the electrodes 10, 25. Thebridge 30, 30 a of atoms from the reactive electrode 25 that is providedby the metal is depicted in FIGS. 2 and 3, in which each circlerepresents an atom of metal, e.g., a silver (Ag) atom and/or a copper(Cu) atom. The dielectric for cation transportation 20 can be asemiconductor or insulator material, which can dissolve ions (providingatoms for the bridge 30, 30 a, and which exhibits electronicconductivity and ionic conductivity due to the dissolution of ions, isarranged between the inert electrode provide by the carbon nanotube 10,and reactive electrode provided by the metal 25. The mobile ions thatprovide the bridge 30, 30 a contained in the dielectric for cationtransportation 20 to change the conductance of the semiconductor orinsulator. The dielectric for cation transportation 20 can have acomposition selected from the group consisting of Ge_(x)Se_(1-x),Ge_(x)S_(1-x), Cu₂S, CuO, Ag₂S, TiO₂, ZrO₂, Ta₂O₅, and SiO₂. The uppersurface of the dielectric for cation transportation 20 can be coplanarwith the upper surface of the oxide layer 5 through which the viadefining the memory cells is formed.

Referring to FIG. 1, the electrode, i.e., reactive electrode 15, thatprovides the metal ions for the bridge 30, 30 a, may be present on theupper surface of the dielectric for cation transportation 20, in whichthe inert electrode provided by the carbon nanotube 10 is present on theoppose lower surface of the dielectric for cation transportation. Thereactive electrode 15 is provided by an electrically conductivematerial, such as a metal, that in response to changes in bias appliedto the two terminal device can diffuse through the dielectric for cationtransportation 20, and therefore change the conductivity through thedielectric for cation transportation 20. In some embodiments, thereactive electrode 15 may be provided by a metal. For example, thereactive electrode 15 may be composed of silver (Ag), copper (Cu),aluminum (Al), zinc (Zn), titanium (Ti), platinum (Pt), palladium (Pd),nickel (Ni) and combinations thereof.

Referring to FIGS. 1-3, in the application of an atomic switch 100 formemory applications, diffusion of metal ions and theirreduction/oxidation processes in the switching operation toform/annihilate a metal atomic bridge 30, 30 a, which is a conductivepath between two electrodes 10, 25, as depicted in FIGS. 2 and 3. FIG. 2depicting atoms having a composition similar to the reactive electrode35 of the atomic switch 100 depicted in FIG. 1 during a first stage ofoperation. FIG. 3 depicts atoms having a composition similar to thereactive electrode 25 of the atomic switch 100 depicted in FIG. 1 duringa second stage of operation. The number of atoms present in theconductive bridge 30 a depicted in FIG. 3 is greater than the number ofatoms that are present in the conductive bridge 30 that is depicted inFIG. 2. In this example, FIG. 1 may represent a low conductivity stateof the atomic switch 100, or an OFF-state (0 state); while FIG. 2 mayrepresent a high conductivity state of the atomic switch 100, or anON-state (1 state); and FIG. 3 may represent an even higher conductivitystate of the atomic switch 100, or an ON state (2 state). Referring toFIGS. 1-3, the use of the carbon nanotube 10 as the inert electrodeallows for the scale of the size of the electrode down to 1 nm, in whichsuch nanometer scale dimensions allows for precise control over theaddition of atoms to the tip of the filament, i.e., end of the bridge30, 30 a in contact with the carbon nanotube 10, for multistage storageapplications. For example, each atom can correspond to an electricalstage of storage. This can provide for applications in memory devices.Further, conversion of the metal atomic bridge 30, 30 a between stagescan be controlled by the bias applied to the electrodes 10, 25. Forexample, a first bias applied to the electrodes 10, 25 can convert themetal atomic bridge 30 in the stage depicted in FIG. 2 to the stage ofthe metal atomic bridge 30 a that is depicted in FIG. 3; and a secondbias, e.g., reverse bias, applied to the electrodes 10, 25 can revertthe metal atomic bridge 30 a from the stage depicted in FIG. 3 to thestage of the metal atomic bridge 30 that is depicted in FIG. 2 or evenFIG. 1.

Some embodiments of the structures depicted in FIGS. 1-3 are now furtherdescribed with a description of some embodiments for methods of formingincluding a Schottky contact composed of a single carbon nanotube 10 tothe channel region of the device, as illustrated with reference to FIGS.4A-7.

FIGS. 4A and 4B depict one embodiment of method step for forming oneembodiment of the atomic switch 100 that is depicted in FIGS. 1-3, inwhich the method includes positioning a nanotube 10 within a trench ofan oxide containing material 4. The oxide containing material 4 may besilicon oxide (SiO₂) that is deposited on a supporting substrate (notshown). The deposition process may be by chemical vapor deposition(CVD). Variations of CVD processes suitable for depositing the oxidecontaining material 4 include, but are not limited to, atmosphericpressure chemical vapor deposition (APCVD), low pressure chemical vapordeposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD),metal organic chemical vapor deposition (MOCVD), and combinationsthereof. Formation of the oxide containing material 4 is not limited toonly chemical vapor deposition methods. For example, the oxidecontaining material 4 may be deposited using spin on deposition, atomiclayer deposition (ALD), thermal growth, e.g., low temperature oxidation,as well as other methods for forming an oxide. In one embodiment, thethickness of the layer for the oxide containing material ranges from 2.0nm to about 500 nm.

The selection of silicon oxide (SiO₂) for the composition of thematerial layer that provides the trench is selected for illustrativepurposes only, and is not intended to limit the present disclosure.Other material compositions for the material layer that provide thetrench are equally applicable so long as the chemical recognitionprocess used for positioning the carbon nanotube is non-selective, i.e.,is not selective to, the composition of the material for the materiallayer that provides the trench.

The trench may be formed in the oxide containing material 4 usingphotolithography and etch processes. Specifically, in one example, aphotoresist mask is formed overlying the oxide containing material 4that provides the trench, in which the portion of the oxide containingmaterial 4 that is underlying the photoresist mask provides thesidewalls for the trench, and exposed portions of the oxide containingmaterial 4, which are not protected by the photoresist mask, are removedusing an etch process, e.g., selective etch process, to form the trench.To provide the photoresist mask, a photoresist layer is first positionedon the layer of the dielectric material that provides dielectric fincap. The photoresist layer may be provided by a blanket layer ofphotoresist material that is formed utilizing a deposition process suchas, for example, chemical vapor deposition, plasma enhanced chemicalvapor deposition, evaporation or spin-on coating. The blanket layer ofphotoresist material is then patterned to provide the photoresist maskutilizing a lithographic process that may include exposing thephotoresist material to a pattern of radiation and developing theexposed photoresist material utilizing a resist developer. Following theformation of the photoresist mask, an etching process may remove theunprotected portions of the oxide containing material 4 that providesthe trench. For example, the transferring of the pattern provided by thephotoresist into the underlying structures may include an anisotropicetch. As used herein, an “anisotropic etch process” denotes a materialremoval process in which the etch rate in the direction normal to thesurface to be etched is greater than in the direction parallel to thesurface to be etched. The anisotropic etch may include reactive-ionetching (RIE). Other examples of anisotropic etching that can be used atthis point of the present invention include ion beam etching, plasmaetching or laser ablation.

Still referring to FIGS. 4A and 4B, following the formation of thetrench, a second dielectric material 15 having a different compositionfrom the first dielectric that provides the trench is deposited withinthe trench. The material composition of the second dielectric material15 is selected so that the chemical recognition process for positioningthe nanotubes 10 within the trench is selective to the second dielectricmaterial. In some examples, the second dielectric material may be ahafnium containing material or an aluminum containing material. Forexample, the second dielectric material 15 may be composed of hafniumoxide (HfO₂), aluminum oxide (Al₂O₃), or other basic metal oxides, or acombination thereof.

The composition of the second dielectric material 15 can be selected tobe bonded with a later deposited monolayer that interacts with ananionic surfactant that encapsulates the carbon nanotube 10 for thechemical recognition process that positions the carbon nanotube 10within the trenches so that the length of the carbon nanotube 10 isparallel to the length of the trenches. It is noted that other materialsmay be suitable for the dielectric layer 15 besides hafnium oxide (HfO₂)and aluminum oxide (Al₂O₃) so long as the material selected provides theselective bonding with the later formed monolayers and surfactant thatis used to align a single carbon nanotube 10. In one preferredembodiment, the second dielectric layer 15 is composed of hafnium oxide(HfO₂). For the purposes of simplicity, and for consistency with FIGS.1-3, the second dielectric layer 15 is hereafter referred to as thehafnium containing layer 15.

The hafnium containing layer 15 can be a deposited using chemical vapordeposition (CVD). Variations of CVD processes suitable for depositingthe hafnium containing layer 15 include, but not limited to, AtmosphericPressure CVD (APCVD), Low Pressure CVD (LPCVD) and Plasma Enhanced CVD(PECVD), Metal-Organic CVD (MOCVD) and combinations thereof. In otherembodiments, the hafnium containing layer 15 may also be deposited usingatomic layer deposition (ALD). Following deposition the hafniumcontaining layer 15 may be patterned to be present only at the base ofthe trenches. The patterning process may include an etch mask providedusing deposition and photolithography in combinations with a selectiveetch process.

Referring to FIGS. 4A, 4B and 5, the method may continue withpositioning a nanotube 10 within the trench using chemical recognitionto the hafnium containing layer 15 (second dielectric material 15). Insome embodiments, chemical recognition includes forming a surfacemonolayer on the second dielectric material and applying a surfactant tothe nanotube, wherein electrostatic force resulting from ion exchangebetween the surface monolayer and the surfactant aligns the nanotube 10within the trench. Referring to FIGS. 4A, 4B and 5, it is noted that asingle, as in one, carbon nanotube 10 is positioned within a trench andin direct contact with the hafnium containing layer 15 to provide theinert electrode of the atomic switch 100 that can provided memoryapplications. However, the process described herein may be applied tomultiple trenches, in which a single nanotube can be aligned with thehafnium containing layer 15 of a single trench, i.e., one nanotube toone trench.

FIG. 5 depicts chemical recognition for engaging the carbon nanotube 10to hafnium containing layer 15 within the trench. The chemicalrecognition process may include forming a surface monolayer on thehafnium containing layer 15 and applying a surfactant to the carbonnanotube 10, wherein electrostatic force resulting from ion exchangebetween the surface monolayer and the surfactant aligns the nanotube 10to the base portion of the trench into direct contact with the surfacemonolayer on the hafnium containing layer 15. The surface monolayer thatmay be formed on the hafnium containing layer 15 through the applicationof 4-(N-hydroxycarboxamido)-I-methylpyridinium iodide (NMPI), whereinthe surface monolayer includes a hydroxamic acid end group that selfassembles on the hafnium containing layer 15. In some embodiments, inwhich the hafnium containing layer 15 is composed of hafnium oxide(HfO₂), the surface monolayer includes a hydroxamic acid end group thatself assembles on the hafnium oxide (HfO₂) but not on silicon oxide(SiO₂), such as the silicon oxide surfaces of the trench.

In some embodiments, the surface monolayer formed on the hafniumcontaining layer 15 can be formed from NMPI molecules that may besynthesized in two steps from the methyl isonicotinate. Methylisonicotinate can be converted to its corresponding hydroxamic acid,4-(N-hydroxycarboxamido)pyridine. Methyl iodide (10 g) can then be addedto a solution of 4-(Nhydroxycarboxamido)pyridine (5.14 g, 0.03 mol) in200 ml of methanol, and the mixture may be stirred at room temperaturefor a time period on the order of approximately 3 days. The precipitateis filtered and washed with methanol and dried. Crystallization from 9:1ethanol-water provides analytically pure pyridinium compound NMPI aslight yellow crystals (7.35 g, 84%).

The surfactant on the carbon nanotube 10 can be provided by sodiumdodecyl sulphate (SDS). The surfactant is an anionic surfactant.Following formation of the surface monolayer on the hafnium containinglayer 15 and encapsulation of the carbon nanotube 10 in the surfactant,the carbon nanotubes and the hafnium containing layer 15 are broughttogether in an aqueous solution during which the chemical recognitionprocess positions a single carbon nanotube 10 within the trench so thatthe length of the carbon nanotube 10 is parallel with the length of thehafnium containing layer, and therefore, the length of the carbonnanotube 10 is aligned to be parallel with the length of the trench.

The carbon nanotubes 10 can be functionalized by positioning the carbonnanotubes in an aqueous solution in which the anionic surfactant, e.g.,SDS, is added or present. The anionic surfactant is not limited to onlySDS, in which the anionic surfactant may also be a carboxylate, asulphonate, a petroleum solphonate, alkybenzenesulphonates,napthalenensulphonate, olefin oils and fats, sulphated esters, sulphatedalkanolamides, and alkylphenols that are either ethoxylated orsulphated. In some embodiments, the anionic surfactant wraps around thecarbon nanotubes 10 leading to strong coulombic attraction between thenegatively charged surfactant and the positively charged monolayer.

In some embodiments, to functionalize the carbon nanotubes 10, asolution of carbon nanotubes is formed with 1% aqueous SDS prepared viahorn sonication. The solution may be then purified using a step-gradientultracentrifugation process. The purified nanotube solution sedimentedat the interface of the two layers while the graphitic impurities andlarge bundles settled to the bottom of the centrifuge tube. The purifiednanotube solution can then be removed via pipette and diluted 1:1 with1% aqueous SDS solution.

In some embodiments, the sequence of monolayer formation on the hafniumcontaining layer 15 and functionalization of the carbon nanotubes 10includes cleaning the hafnium containing layer 15 by oxygen plasma at300 mtorr for 5 min. In one example, the NMPI monolayer may then beassembled on the exposed surface of the hafnium containing layer 15 byplacing the structure including the hafnium containing layer 15 in a 3.5mM solution of NMPI (3:1 ethanol/water) for a time period on the orderof approximately 1 hour (h). The surface of the hafnium containing layer15 may then be rinsed with ethanol. The structure, i.e., trenchcontaining structure having the hafnium containing layer 15 presenttherein, can then be positioned horizontally with its surface facingupwards in a dialysed nanotube solution for 1 h, without an agitation. Asingle carbon nanotubes 10 selectively deposits on the exposed portionof the hafnium containing layer 15 within the trench. After nanotubedeposition, the structure can be rinsed flowing deionized water for 30seconds and subsequently rinsing the structures in a sonication bathwith deionized water for 1 min.

It is noted that the above description provides one example of achemical recognition process that can position a nanotube 10 on thesurface of the dielectric layer 15 that is overlying the type III-Vsemiconductor substrate 1 and is between the ohmic contacts 4, 5. Theoxide material 20 that provides the trench 25 does not interact with thechemical recognition process, and the dimensions of the trench 25facilitate the positioning of the longest dimension L1 of the carbonnanotube 10 to be perpendicular to the gate length. In addition to thechemical recognition process for depositing the single carbon nanotube10 within the trench 25, the trench dimensions of the repulsive force ofthe negatively charged carbon nanotubes 10 provides that only one singlecarbon nanotube 10 can be positioned in the trench 25.

FIG. 5 illustrates the formation of the monolayer on a dielectric layerof hafnium oxide (HfO₂) using NMPI. FIG. 5 also illustrates the carbonnanotube 10 being functionalized with SDS. FIG. 5 depicts the Coulombicreaction between the monolayer formed from NMPI and the carbon nanotube10 that has been functionalized with SDS that positions the carbonnanotube 10 within the trench. As noted above, the nanotube 10 can be asingle walled carbon nanotube (SWCNT) having a diameter D1 ranging from1 nm to 2 nm, and a length that ranges from about 0.5 nanometers toabout 10 microns.

FIG. 6 depicts patterning a via 6 to the carbon nanotube 10, wherein thevia 6 to the nanotube 10 defines a memory cell. In some embodiments,forming the via 6 may begin with deposition an oxide layer 5, such assilicon oxide (SiO₂), on the surface of the structure depicted in FIGS.4A and 4B. The deposition process may include chemical vapor deposition,such as Atmospheric Pressure CVD (APCVD), Low Pressure CVD (LPCVD) andPlasma Enhanced CVD (PECVD), Metal-Organic CVD (MOCVD) and combinationsthereof. In other embodiments, the oxide layer 5 may be deposited usingspin on deposition. It is further noted, that the oxide composition forthe oxide layer 5, such as silicon oxide, is provided for illustrativepurposes, and is not intended to limit the present disclosure.Additionally other types of dielectrics can be substituted for the oxidelayer 5. For example, in other embodiments, other interlevel dielectricmaterials can be substituted for the silicon oxide composition that isdescribed above for the oxide layer 5, such as nitrides, e.g., siliconnitride (Si₃N₄).

Following deposition, the oxide layer 5 may be patterned and etched toprovide the via 6. The via extends through the entire thickness andexposes a portion of the carbon nanotube 10. The pattern and etchprocessed for forming the via 6 are similar to those for forming thetrench, as described above with reference to FIGS. 4A and 4B. However,when etching the oxide layer 5, in some embodiments, the etch chemistrymay be selective to the carbon nanotube 10. This provides that thematerial removed from the oxide layer 5 to provide the via 6 does notremove the carbon nanotube 10.

FIG. 7 depicts depositing a dielectric for cation transportation 20within the via 6 on the carbon nanotube 10. In some examples, thedielectric for cation transportation 20 has a composition selected fromthe group consisting of Ge_(x)Se_(1-x), Ge_(x)S_(1-x), Cu₂S, CuO, Ag₂S,and SiO₂. The deposition process for filling the via with the dielectricfor cation transportation 20 may include chemical vapor deposition, suchas Atmospheric Pressure CVD (APCVD), Low Pressure CVD (LPCVD) and PlasmaEnhanced CVD (PECVD), Metal-Organic CVD (MOCVD) and combinationsthereof. In other examples, the deposition process for filling the viawith the dielectric for cation transportation 20 may include dipcoating, spin-coating, brush coating, chemical solution deposition,physical vapor deposition, and plating. In some embodiments, followingdeposition, to provide that the upper surface of the dielectric forcation transportation 20 is coplanar with the upper surface of the oxidelayer 6 through which the via 6 is formed, the upper surface of thedielectric for cation transportation 20 may be planarized. In oneexample, the upper surface of the dielectric for cation transportation20 may be planarized by chemical mechanical planarization (CMP).

Referring to FIG. 1, in a following process step, a second electrode,i.e., reactive electrode 25, is formed on the dielectric for cationtransportation 20. The second electrode is composed of a metal. In someexamples, the second electrode may have a composition that is selectedfrom the group consisting of silver (Ag), copper (Cu), aluminum (Al),zinc (Zn) and combinations thereof.

The second electrode, i.e., reactive electrode 25, may be formed bydepositing a metal layer, e.g., blanket depositing, on the upper surfaceof the dielectric for cation transportation 20, and then patterning andetching the deposited metal layer to remove the portion of the layerthat is not present over the dielectric for cation transportation 20.The metal layer that provides the second electrode, i.e., reactiveelectrode 25, may be deposited using a physical vapor depositionprocess, such as plating, electroplating, electroless plating,sputtering and combinations thereof. In other embodiments, the metallayer may be deposited using chemical vapor deposition and/or atomiclayer deposition.

Following deposition of the metal layer, a pattern and etch processremoves the portion of the metal layer that is not present over thedielectric for cation transportation 20. Specifically, a pattern isproduced by applying a photoresist to the surface to be etched; exposingthe photoresist to a pattern of radiation; and then developing thepattern into the photoresist utilizing a resist developer. Once thepatterning of the photoresist is completed, the sections of the metallayer covered by the photoresist are protected, while the exposedregions of the metal layer are removed using a selective etching processthat removes the unprotected regions. The portions of the metal layerthat remain following the etch step provides the second electrode, i.e.,reactive electrode 25. The selective etch process may be an anisotropicetch, such as reactive ion etch, or an isotropic etch, such as a wetchemical etch. Next the photoresist pattern is removed.

It is to be understood that aspects of the present invention will bedescribed in terms of a given illustrative architecture; however, otherarchitectures, structures, substrate materials and process features andsteps can be varied within the scope of aspects of the presentinvention.

The present embodiments can include a design for an integrated circuitchip, which can be created in a graphical computer programming language,and stored in a computer storage medium (such as a disk, tape, physicalhard drive, or virtual hard drive such as in a storage access network).If the designer does not fabricate chips or the photolithographic masksused to fabricate chips, the designer can transmit the resulting designby physical means (e.g., by providing a copy of the storage mediumstoring the design) or electronically (e.g., through the Internet) tosuch entities, directly or indirectly. The stored design is thenconverted into the appropriate format (e.g., GDSII) for the fabricationof photolithographic masks, which typically include multiple copies ofthe chip design in question that are to be formed on a wafer. Thephotolithographic masks are utilized to define areas of the wafer(and/or the layers thereon) to be etched or otherwise processed.

Methods as described herein can be used in the fabrication of integratedcircuit chips. The resulting integrated circuit chips can be distributedby the fabricator in raw wafer form (that is, as a single wafer that hasmultiple unpackaged chips), as a bare die, or in a packaged form. In thelatter case, the chip is mounted in a single chip package (such as aplastic carrier, with leads that are affixed to a motherboard or otherhigher level carrier) or in a multichip package (such as a ceramiccarrier that has either or both surface interconnections or buriedinterconnections). In any case, the chip is then integrated with otherchips, discrete circuit elements, and/or other signal processing devicesas part of either (a) an intermediate product, such as a motherboard, or(b) an end product. The end product can be any product that includesintegrated circuit chips, ranging from toys and other low-endapplications to advanced computer products having a display, a keyboardor other input device, and a central processor.

It is to be appreciated that the use of any of the following “/”,“and/or”, and “at least one of”, for example, in the cases of “A/B”, “Aand/or B” and “at least one of A and B”, is intended to encompass theselection of the first listed option (A) only, or the selection of thesecond listed option (B) only, or the selection of both options (A andB). As a further example, in the cases of “A, B, and/or C” and “at leastone of A, B, and C”, such phrasing is intended to encompass theselection of the first listed option (A) only, or the selection of thesecond listed option (B) only, or the selection of the third listedoption (C) only, or the selection of the first and the second listedoptions (A and B) only, or the selection of the first and third listedoptions (A and C) only, or the selection of the second and third listedoptions (B and C) only, or the selection of all three options (A and Band C). This may be extended, as readily apparent by one of ordinaryskill in this and related arts, for as many items listed.

Having described preferred embodiments of a scaled nanotube electrodefor a low power multistage atomic switch (which are intended to beillustrative and not limiting), it is noted that modifications andvariations can be made by persons skilled in the art in light of theabove teachings. It is therefore to be understood that changes may bemade in the particular embodiments disclosed which are within the scopeof the invention as outlined by the appended claims. Having thusdescribed aspects of the invention, with the details and particularityrequired by the patent laws, what is claimed and desired protected byLetters Patent is set forth in the appended claims.

1.-5. (canceled)
 6. A method of forming a memory device comprising:positioning a carbon nanotube within a trench of an oxide containingmaterial; patterning the trench to provide a via to the carbon nanotube,wherein the via to the carbon nanotubes defines a memory cell;depositing a dielectric for cation transportation within the trench onthe carbon nanotube; and forming an electrode on the dielectric forcation transportation, wherein the second electrode is composed of ametal.
 7. The method of claim 6, wherein the carbon nanotube is a singlewall carbon nanotube (SWCNT) having a diameter D1 ranging from 1 nm to 2nm, and a length that ranges from about 0.5 nanometers to about 10microns.
 8. The method of claim 6, wherein the dielectric for cationtransportation has a composition selected from the group consisting ofGe_(x)Se_(1-x), Ge_(x)S_(1-x), Cu₂S, CuO, Ag₂S, TiO₂, ZrO₂, Ta₂O₅, andSiO₂.
 9. The method of claim 6, wherein the electrode is of said metalhaving a composition selected from the group consisting of silver (Ag),copper (Cu), aluminum (Al), zinc (Zn) and combinations thereof.
 10. Amethod of forming a memory device comprising: depositing a seconddielectric material within a trench of composed of a first dielectricmaterial; positioning a nanotube within the trench using chemicalrecognition to the trench dielectric material; depositing a dielectricfor cation transportation within the trench on the nanotube; and formingan electrode on the dielectric for cation transportation, wherein theelectrode is composed of a metal.
 11. The method of claim 10, whereinthe second dielectric material comprises a hafnium including oxide. 12.The method of claim 10, wherein the first dielectric material comprisesa silicon including oxide.
 13. The method of claim 10, wherein saidchemical recognition comprises forming a surface monolayer on the firstdielectric material and applying a surfactant to the nanotube, whereinelectrostatic force resulting from ion exchange between the surfacemonolayer and the surfactant aligns the nanotube within the trench. 14.The method of claim 13, wherein the surface monolayer is formed from4-(N-hydroxycarboxamido)-I-methylpyridinium iodide (NMPI).
 15. Themethod of claim 13, wherein surface monolayer includes a hydroxamic acidend group that self assembles on the second dielectric material.
 16. Themethod of claim 14, wherein the surfactant on the nanotube is providedby sodium dodecyl sulphate (SDS).
 17. The method of claim 10, whereinthe nanotube is a single wall carbon nanotube (SWCNT) having a diameterD1 ranging from 1 nm to 2 nm.
 18. The method of claim 10, wherein thenanotube has a length that ranges from about 0.5 nanometers to about 10microns.
 19. The method of claim 10, wherein the dielectric for cationtransportation has a composition selected from the group consisting ofGe_(x)Se_(1-x), Ge_(x)S_(1-x), Cu₂S, CuO, Ag₂S, TiO₂, ZrO₂, Ta₂O₅, andSiO₂.
 20. The method of claim 10, wherein the electrode is of said metalhaving a composition selected from the group consisting of silver (Ag),copper (Cu), aluminum (Al), zinc (Zn) and combinations thereof.